Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

• the present invention relates to a method for producing stabilized Olefin polymers, during the polymerization a stabilizer and optionally further additives can be added.
• the invention also relates to those so produced Olefin polymers.
• the low pressure polymerization of olefins using organometallic complex catalysts usually leads to a fine powdery Polymer that is granulated in an extruder before shaping.
• organometallic complex catalysts e.g. Ziegler-Natta catalysts
• substances such as stabilizers, Corrosion-preventing compounds, color improvers, antistatic agents or others Processing aids added.
• this granulation is not always desirable or possible, such as with high molecular weight polymers.
• transition metal catalysts solid Supported catalysts
• Preferred compounds within the framework of the above constitution are those in which R in the phenyl ring is in the ortho position to the phosphite oxygen.
• the groups R and R1 are preferably straight-chain or branched alkyl with 4-8 carbon atoms, such as n-butyl, sec-butyl, tert-butyl, tert-pentyl, 2-ethylhexyl, n-octyl and 1,1,3,3-tetramethylbutyl. Particularly preferred are the groups tert-butyl, tert-pentyl and 1,1,3,3-tetramethylbutyl. Furthermore, the group R1 is particularly preferably in the para position to the oxygen, especially when R1 is tert-alkyl.
• R1 can be hydrogen or alkyl having 1 to 18 carbon atoms, but it is preferably for an Alkl distr with 1 to 8 carbon atoms, which are either straight-chain or branched. Tert-alkyl having 4 to 8 carbon atoms is particularly preferred.
• R2 is preferably a direct bond or alkylene of the formula wherein R5 and R6 are independently hydrogen, alkyl having 1 to 7 carbon atoms or aryl, with the proviso that the total number of carbon atoms does not exceed 12.
• Typical aryl groups include phenyl, tolyl, mesityl, xylyl and 1- and 2-naphthyl.
• R2 is particularly preferably a direct bond, methylene or ethylidene.
• R3 and R4 are preferably alkyl having 1 to 4 carbon atoms.
• A is preferably ethylene or trimethylene.
• Very particularly preferred compounds according to the invention are N-methyliminodiethanol-bis- (3,3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite and specially 2,2 ', 2 "-Nitrilotriethanol-tris- (3,3', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite.
• 0.005 to 0.5% by weight are used, based on the polymer to aminoalkyl-1,1'-biphenyl-2,2'-diyl-phosphite or Aminoalkyl-2,2'-alkylidene-bis (phenyl) phosphite.
• the olefins polymerizable by this process are ethylene and ⁇ -olefins such as e.g. Propylene, 1-butene, 4-methylpentene-1,5-methylhexene-1 or styrene, and mixtures of Olefins such as ethylene-propylene or propylene in a mixture with smaller amounts higher alpha olefins.
• Preferred here are C2 or C3 olefins, their copolymers and Styrene.
• high molecular weight PE is a PE with a high molecular weight i.e. MW greater than 250,000 or melt index less than 1 g / 10 min at 5 kg and 190 ° C to understand.
• the related polymerization catalysts are transition metal catalysts. It In addition to the classic Ziegler catalysts, solid ones are also preferred Supported catalysts in question. Supported catalysts that can be used exist, for example from a compound of a transition metal (such as an element of subgroup IV, for example titanium, zirconium or hafnium, or chromium) and a solid support (such as a magnesium halide, aluminum oxide, or silicon dioxide).
• a transition metal such as an element of subgroup IV, for example titanium, zirconium or hafnium, or chromium
• a solid support such as a magnesium halide, aluminum oxide, or silicon dioxide.
• Solid supported catalysts of an element of subgroup IV exist, for example from an anhydrous magnesium dihalide in active form and a Titanium compound. There are also catalysts with the other metals IV subgroup (Zr and Hf) in question. Taking magnesium dihalide is in active form to understand such a line of strongest reflection in its X-ray spectrum is wider than the corresponding line in the spectrum of the inactive Magnesium dihalide.
• the preferred magnesium dihalide Magnesium dichloride or magnesium dibromide related.
• the titanium compound contains preferably at least one titanium-halogen bond, particularly preferably used one titanium tetrachloride.
• the titanium compound can be used in combination with a Electron donor are used, for example a carboxylic acid ester, as described in EP-A-0 045 977, or an aliphatic ether as described in EP-A-0 045 977 EP-A-0 361 494 is described.
• a Electron donor for example a carboxylic acid ester, as described in EP-A-0 045 977, or an aliphatic ether as described in EP-A-0 045 977 EP-A-0 361 494 is described.
• the electron donor is expediently washed out with an inert solvent, for example with hexane or heptane.
• the catalyst prepared in this way is activated by Reaction with an aluminum compound which carries at least one alkyl radical is preferably used as a solution in an alkane.
• Aluminum alkyls examples are Al (C2H5) 3 or Al (C4H9) 3.
• a coactivator Add electron donor such as an organic silicon compound that contains at least contains a Si-O-C bond, as described, for example, in EP-A-0 045 977.
• silicon compounds examples include phenyltriethoxysilane, Phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, Dimethyldiethoxysilane, ethyltrimethoxysilane, cyclohexyltriethoxysilane, Dicyclohexyldiethoxysilane, cyclohexyltrimethoxysilane or dicyclohexyldimethoxysilane.
• transition metal catalysts consist, for example, of a chromium compound which is applied to a solid support, for example aluminum oxide or silicon dioxide or mixtures thereof.
• a chromium compound which is applied to a solid support, for example aluminum oxide or silicon dioxide or mixtures thereof.
• a chromium salt solution eg chromium trichloride or chromium trioxide in water.
• the amount of chromium is determined so that the silica gel is covered with about 0.1 to 3% chromium (preferably about 1% chromium), the amount of water used corresponds to the pore volume of the silica gel.
• alumina In addition to silica gel, other carriers can be used, such as alumina, alumina-silica, aluminum phosphates (EP 215336, WRGrace & Co.), the surface of which can be modified (e.g. fluorine-containing carriers, US 4011382, Union Carbide).
• the supports are designed in such a way that, after activation with dry air or oxygen, they have a surface area of more than 50 m2 / g and a pore volume of more than 0.5 ml / g.
• chromium / titanium or chromium / iron mixtures can also be used (US 4011382, Union Carbide, DE 2210959, US 4041224, Chemplex Co.).
• the chromium-coated supports are usually activated in dry air or oxygen at temperatures of 500 to about 1000 ° C., temperatures of 700 to 900 ° C. being preferred. It is assumed that the chromium compound is then present as chromium VI. After the oxygen treatment, these catalysts can be activated with CO or ethylene. The activation takes place below a temperature of 500 ° C, preferred temperatures are 200-350 ° C. The chromium compound is reduced to chromium II to IV. The catalysts activated in this way have no induction time. Without this activation, the activation occurs during the polymerization. An induction time is often observed in the batch process.
• the active chromium compound can also be applied to a support as an organochromium compound, for example chromocene dichloride (WL Carrick, et al., J. Polym. Sci., A1, 10, 2609-2620 (1972), FJ Karol, et al., J Polym Sci., A1, 10, 2621-2637 (1972), DE 2802517, US 3709853, DE 2742543, Union Carbide).
• organochromium compound for example chromocene dichloride
• the polymerization with these catalysts can be carried out in liquid by known methods or in the gaseous phase.
• the liquid phase can e.g. be aliphatic hydrocarbon or the liquid monomer itself.
• the aminoalkyl-1,1'-biphenyl-2,2'-diyl-phosphites or Aminoalkyl-2,2'-alkylidene-bis (phenyl) -phosphites at the beginning, during or towards the end the polymerization added to the polymerization medium.
• the compounds mentioned and, if appropriate, the further additives preferably added at the beginning continuous polymerizations are the compounds mentioned and if necessary, the further additives are also added continuously; either separately or together with the monomers.
• the method according to the invention is preferred using additional Stabilizers carried out.
• a particularly preferred embodiment of the invention is the above method under carry out additional addition of at least one compound, which at least has a 2,2,6,6-tetramethylpiperidine residue or with additional addition at least one antioxidant of the sterically hindered phenol type, the joint use of such a 2,2,6,6-tetramethylpiperidine compound with a phenol is particularly preferred.
• the Polymerization even with the addition of at least one under the reaction conditions no water-releasing compound from the series of hydrotalcites, zeolites, Metal soaps, metal carbonates or metal oxides are made.
• the sterically hindered amines are primarily known as light stabilizers, but here they also act as antioxidants, ie they give the polymer thermal-oxidative stability.
• These compounds contain the group of formula I. once or several times. They can be compounds of relatively low molecular weight ( ⁇ 700) or of higher molecular weight. In the latter case, the products can also be oligomeric or polymeric.
• substituents are C1-C12-alkyl, they represent, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
• R2 can e.g. nor represent, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
• R1 is C3-C8-alkenyl, it can be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 4-tert.-butyl-2-butenyl.
• R1 is preferably propargyl.
• R1 is especially phenethyl and especially benzyl.
• R1 is as C1-C8-alkanoyl, for example, formyl, propionyl, butyryl, octanoyl, but preferably acetyl and, as C3-C5-alkenoyl, especially acryloyl.
• R2 is a monovalent radical of a carboxylic acid, it represents, for example, a Acetic acid, caproic acid, stearic acid, acrylic acid, methacrylic acid, benzoic or ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid residue.
• R2 is a divalent radical of a dicarboxylic acid, it represents, for example a malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, Sebacic acid, maleic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid, Butyl- (3,5-di-tert-butyl-4-hydroxybenzyl) -malonic acid or Bicycloheptenedicarboxylic acid residue.
• R2 represents a trivalent radical of a tricarboxylic acid, it means, for example, one Trimellitic acid or a nitrilotriacetic acid residue.
• R2 represents a tetravalent radical of a tetracarboxylic acid, it means, for example, the tetravalent radical of butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid.
• R2 is a divalent radical of a dicarbamic acid, it represents, for example a hexamethylene dicarbamic acid or a 2,4-toluylene dicarbamic acid residue.
• n is the number 1 or 2
• R1 has the meaning given under a
• R3 is hydrogen, C1-C12-alkyl, C2-C5-hydroxyalkyl, C5-C7-CycloaBy7, C7-C8-aralkyl, C2-C18-alkanoyl , C3-C5-alkenoyl or benzoyl and R4 when n is 1 is hydrogen, C1-C18-alkyl, C3-C8-alkenyl, C5-C7-cycloalkyl, C1 substituted with a hydroxy, cyano, alkoxycarbonyl or carbamide group -C4-alkyl, glycidyl, a group of the formula -CH2-CH (OH) -Z or of the formula -CONH-Z, in which Z is hydrogen, methyl or phenyl; when n is 2, C2-C12-alkylene, C6-C12-ary
• any substituents are C5-C7-cycloalkyl, they are in particular cyclohexyl represent.
• R3 is in particular phenylethyl or especially benzyl.
• R3 is in particular 2-hydroxyethyl or 2-hydroxypropyl.
• R3 is as C2-C18-alkanoyl, for example propionyl, butyryl, octanoyl, dodecanoyl, Hexadecanoyl, octadecanoyl, but preferably acetyl and as C3-C5-alkenoyl especially acryloyl.
• R4 means C2-C8-alkenyl, then it is e.g. allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.
• R4 as substituted with a hydroxy, cyano, alkoxycarbonyl or carbamide group C1-C4-alkyl can, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, Methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2- (dimethylaminocarbonyl) -ethyl.
• substituents are C2-C12-alkylene, it is, for example, ethylene, Propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, Decamethylene or dodecamethylene.
• substituents are C6-C15-arylene, they represent, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
• D is in particular cyclohexylene.
• n is the number 1 or 2
• R1 has the meaning given under a) and R5, when n is 1, C2-C8-alkylene or C2-C8-hydroxyalkylene or C4-C22-acyloxyalkylene, and when n is 2, the Is group (-CH2) 2C (CH2-) 2.
• R5 is C2-C8-alkylene or hydroxyalkylene, it is, for example, ethylene, 1-methyl-ethylene, propylene, 2-ethyl-propylene or 2-ethyl-2-hydroxymethylpropylene.
• R5 is, for example, 2-ethyl-2-acetoxymethylpropylene.
• R6 is hydrogen, C1-C12-alkyl, allyl, benzyl, glycidyl or C2-C6-alkoxyalkyl and R7, when n is 1, is hydrogen, C1 -C12-alkyl, C3-C5-alkenyl, C7-C9-aralkyl, C5-C7-cycloalkyl, C2-C4-hydroxyalkyl, C2-C6-alkoxyalkyl, C6-C0-aryl, glycidyl or a group of the formula - (CH2 ) p-COO-Q or of the formula - (CH2) pO-CO-Q, wherein p is 1 or 2 and Q is C1-C4-alkyl or phenyl, when n is 2, C2-C12-alkylene, C4-C12
• substituents are C1-C12-alkyl, they represent, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
• C1-C18-alkyl can, for example, the above listed groups and also, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or represent n-octadecyl.
• substituents are C2-C6-alkoxyalkyl, they represent e.g. methoxymethyl, Ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.
• R7 represents C3-C5-alkenyl, it means, for example, 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.
• R7, T1 and T2 are especially phenethyl or especially benzyl. If T1 and T2 together with the C atom form a cycloalkane ring, this can be, for example Be cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.
• R7 is C2-C4-hydroxyalkyl, it represents e.g. 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
• R7, T1 and T2 are in particular phenyl, ⁇ - or ⁇ -naphthyl, the are optionally substituted by halogen or C1-C4-alkyl.
• R7 represents C2-C12-alkylene, it is e.g. ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or Dodecamethylene.
• R7 is in particular 2-butenylene, 2-pentenylene or 3-hexenylene.
• R7 is C6-C12-arylene, it is, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
• Z ' is C2-C12-alkanoyl, it represents, for example, propionyl, butyryl, octanoyl, Dodecanoyl, but preferably acetyl.
• D has as C2-C10-alkylene, C6-C15-arylene or C6-C12-cycloalkylene under b) given meaning.
• any substituents C1-C12-alkyl they represent, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
• substituents are C1-C4-hydroxyalkyl, they represent e.g. 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
• A is C2-C6-alkylene, it represents, for example, ethylene, propylene, 2,2-dimethylpropylene, Tetramethylene or hexamethylene.
• R11 and R12 together represent C4-C5-alkylene or oxaalkylene, this means e.g. Tetramethylene, pentamethylene or 3-oxapentamethylene.
• Oligomeric or polymeric compounds whose repeating structural unit is a or contains more than one 2,2,6,6-tetraalkylpiperidine radicals of the formula (I), in particular Polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, Polyaminotriazines, poly (meth) acrylates, polysiloxanes, poly (meth) acrylamides and their Copolymers containing such radicals.
• classes e) and f) are particularly suitable, especially those Tetraalkylpiperidine compounds containing s-triazine groups. Furthermore are connections 74, 76, 84, 87, 92 and 95 are particularly suitable.
• the amount of the addition of the tetramethylpiperidine compound depends on the desired degree of stabilization. In general, 0.01 to 0.5% by weight is used, in particular 0.05 to 0.3% by weight, based on the polymer.
• the amount of added antioxidant depends on the amount of Aminoalkyl-1,1'-biphenyl-2,2'-diyl-phosphite or aminoalkyl-2,2'-alkylidene-bis (phenyl) -phosphite. In general, 0.005 to 0.5% by weight, especially 0.01 up to 0.1% by weight, based on the polymer, added.
• usable compounds from the series of hydrotalcites, zeolites, Metal soaps, metal carbonates, or metal oxides are both naturally occurring Minerals as well as synthetically produced compounds.
• a n- is preferably OH ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , ClO4 ⁇ , HCO3 ⁇ , CH3COO ⁇ , C6H5COO ⁇ , CO3 2 ⁇ , SO4 2 ⁇ , (CHOHCOO) 22 ⁇ , (CHOH) 4CH2OHCOO ⁇ .
• hydrotalcites which can conveniently be used in the process as described above are compounds with the general formula Xa, M 2+ / xAl2 (OH) 2x + 6nz (A n- ) 2 • mH2O where in the present formula Xa M2+ represents at least one metal from the series of Mg and Zn and Mg2+ is preferred,
• a n- is an anion, for example from the series of CO3 2 ⁇ , OH ⁇ and S2 ⁇ , where n is the valence of the anion, m is a positive number, preferably from 0.5 to 5, and x and z are positive numbers, where x is preferably 2 to 6 and z is less than 2 .
• hydrotalcites are DHT-4A and DHT-4C Kyowa company, Japan.
• Hydrotalcites of the formulas are very particularly preferred Al2O3 ⁇ 6MgO ⁇ CO2 ⁇ 12H2O, Mg 4.5 Al2 (OH) 13 ⁇ CO3 ⁇ 3.5H2O, 4MgO ⁇ Al2O3 ⁇ CO2 ⁇ 9H2O, 4MgO ⁇ Al2O3 ⁇ CO2 ⁇ 6H2O, ZnO ⁇ 3MgO ⁇ Al2O3 ⁇ CO2 ⁇ 8-9H2O or ZnO ⁇ 3MgO ⁇ Al2O3 ⁇ CO2 ⁇ 5-6H2O.
• the preferred per se known zeolites which are used in the above process have an average effective pore diameter of 3-5 ⁇ on, those of the NaA type having an average effective pore diameter of 4 ⁇ , which is why they are also referred to as zeolites 4A.
• zeolites examples include the compounds: Na12 [(AlO2) 12 (SiO2) 12] ⁇ 12H2O Ca 4.5 Na3 [(AlO2) 12 (SiO2) 12] ⁇ 30H2O K9Na3 [(AlO2) 12 (SiO2) 12] ⁇ 27H2O
• Preferred and commercially available zeolites are molecular sieves.
• metal soaps can also be used.
• Metal soaps of divalent metals with fatty acids containing 8-28 carbon atoms exhibit.
• Metal soaps of calcium are particularly preferred, with calcium stearate and calcium pelargonate is most preferred.
• metal carbonates or metal oxides can also be used.
• Oxides of divalent metals are preferred.
• Oxides of the metals are particularly preferred of the second main or sub-group, with zinc and magnesium oxide being very special is preferred.
• the compounds that can be used according to the invention are not or only weakly bound water at 50-800 ° C, preferably 80-400 ° C, dried, provided they are not already sufficiently dried and stored under exclusion of moisture became.
• the drying can take place in a vacuum or under inert gas.
• the surfaces of the substances can with surface-active reagents, such as carboxylic acids or linear alcohols with 8 or more carbon atoms, e.g. stearic acid.
• the compounds from the which do not release water under the reaction conditions Series of hydrotalcites, zeolites, metal soaps, metal carbonates, or metal oxides similar synthetic compounds are generally used in an amount from 0.005 to 0.2% by weight, based on the polymer, added, preferably in one Amount from 0.01 to 0.1% by weight.
• Another object of the present invention is the use of the above defined aminoalkyl-1,1'-biphenyl-2,2'-diyl-phosphites or aminoalkyl-2,2'-alkylidene-bis (phenyl) -phosphites in a process for the polymerization of Olefins on a transition metal catalyst to stabilize the thus obtainable Polymers.
• the preferences of the method apply here analogously.
• Another object of the present invention are those according to the above defined process available polyolefins.
• the preferences of the procedure apply here analogously.
• the polyolefins produced according to the invention are particularly suitable for the production of Semi-finished products (plates, tubes and profiles of any cross-section) and for the following Manufacturing process: rotational molding, centrifugal casting, injection molding, Thermoplastic foam casting, transfer molding, pressing, sintering, calendering, extrusion, Hollow body blow molding, extrusion stretch blow molding, casting of hollow bodies, spinning, Foaming, powder coating, coating and cable sheathing.
• a 3-1 steel autoclave is evacuated at 110 ° C for half an hour, then at the same Temperature purged with gaseous propylene.
• the autoclave is cooled to 20 ° C, and one after the other are the additives (as a powder) and the catalyst (30 mg, which was previously with 0.4 ml of triethylaluminum in 25 ml of hexane was contacted for 10 minutes).
• the autoclave is closed, 0.1 bar hydrogen is released and 650 g liquid Propylene is added, the stirrer switched on and the temperature increased to 70.degree.
• the pressure in the autoclave is released, 10 ml of isopropanol are added and Stirred at 70 ° C. for 30 min.
• the polymer is removed and at 80 ° C overnight Vacuum dried. Yield around 300 g.
• the granules are pressed at 230 ° C. to give sheets 1 mm thick.
• the panels are in Water stored at a temperature of 90 ° C and the yellowing observed.
• the sample stabilized according to the invention with 0.1% AP-1 shows very good processing properties and is significantly less discolored in comparison to the unstabilized sample and in comparison to the sample stabilized with 0.1% VP-1 or VP-2.
• Additive Amount [mg] PP yield G II 1a no 0 305 95 1b Irgafos 12 150 310 95 1c Irgafos 168 150 300 95 1d Ultranox 626 150 305 95 1e Irgafos 12+ 150+ 300 95 Chimassorb 944 300 1f Irgafos 12+ 150+ 305 95 Irganox 1330 150
• I.I . Isotacticity index (% of the PP insoluble in boiling heptane)
• Irgafos 12 does not affect the polymerisation.
• the 5 PP samples are extruded three times on a single screw extruder.
• the temperature of the last zone was 280 ° C.
• the samples are each additionally stabilized with 0.1% Irganox 1010® (pentaerythrityl-tetrakis (3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl] propionate) and 0.1% calcium stearate.
• Irganox 1010® penentaerythrityl-tetrakis (3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl] propionate
• the sample stabilized with Irgafos 12 shows the best color and stability in heat aging at 135 ° C.
• YI Yellowness Index after 0, 1, 2 and 4 weeks of water storage
• the sample stabilized with Irgafos 12 shows the least discoloration in the Hot water storage.
• magnesium ethylate (Mg (OC2H5) 2) are 30 ml of toluene and at room temperature 30 ml of titanium tetrachloride are added.
• the suspension is heated to 130 ° C. with stirring and stirred at this temperature for half an hour and filtered hot.
• the arrears will with 30 ml of toluene and 30 ml of titanium tetrachloride were added, and the mixture was stirred at 130 ° C. for half an hour and filtered hot.
• the residue is mixed with 30 ml of toluene and 30 ml of titanium tetrachloride, Stirred for one hour at 130 ° C and filtered hot. Then the residue washed five times with 50 ml of hexane and dried.
• the catalyst contains 2% titanium, 15% magnesium, 58% chlorine.
• a 3-1 steel autoclave is evacuated at 110 ° C for half an hour, then at the same Temperature flushed with ethylene.
• the autoclave is cooled to 20 ° C, and 1 l of heptane, the additives (as powder) and the catalyst (30 mg, the was previously contacted with 0.4 ml of triethylaluminum in 25 ml of hexane for 10 min) admitted.
• the autoclave is closed, 2 bar hydrogen and ethylene to one Total pressure of 10 bar given up, the stirrer switched on and the temperature up 80 ° C increased.
• the pressure in the autoclave is released and 10 ml of isopropanol are added added and stirred at 70 ° C. for 30 min.
• the polymer is removed, hexane is im Rotovap removed and the polymer dried at 80 ° C overnight in a vacuum.
• the Yield is 200 g.
• 38 g of the polyethylene thus obtained are with the addition of 0.1% Irganox 1010 and 0.1% calcium stearate for 10 minutes in a Brabender plastograph at 180 ° C kneaded. The mass is then pressed at 200 ° C into a 1 mm thick plate and in Water stored at a temperature of 90 ° C. One determines the resulting Yellowing.
• a catalyst with 1% Cr on silica gel is activated with oxygen at 900 ° C.
• a 3-1 steel autoclave is evacuated at 110 ° C for half an hour, then at the same Temperature flushed with ethylene.
• the autoclave is cooled to 20 ° C, and one after the other 1 l of heptane, the additives (as powder) and approx. 100 mg of catalyst are added.
• ethylene is added to a total pressure of 14 bar, the stirrer switched on and the temperature increased to 90.degree.
• the pressure in the autoclave is released, 10 ml of isopropanol are added and the mixture is stirred at 70 ° C. for 30 minutes.
• the polymer is removed, heptane is removed in the Rotovap and the polymer is added 80 ° C dried overnight in a vacuum.
• the yield is 200 g.
• 38 g of the polyethylene obtained in this way are kneaded in a Brabender plastograph at 180 ° C. for 10 minutes with the addition of 0.1% Irganox 1010 and 0.1% calcium stearate.
• the mass is then pressed at 200.degree. C. into a 1 mm thick plate and stored in water at a temperature of 90.degree. The resulting yellowing is determined.
• the sample stabilized according to the invention with 0.1% AP-1 shows very good processing properties and is significantly less discolored than the sample stabilized with 0.1% VP-1.
• the sample stabilized with Irgafos 12 yellows significantly less than the comparison sample.

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• 1995
  • 1995-10-24 EP EP95810655A patent/EP0710677A3/fr not_active Withdrawn
  • 1995-10-26 US US08/548,838 patent/US5650464A/en not_active Expired - Fee Related
  • 1995-10-31 SK SK1367-95A patent/SK136795A3/sk unknown
  • 1995-11-01 CZ CZ952861A patent/CZ286195A3/cs unknown
  • 1995-11-01 BR BR9505055A patent/BR9505055A/pt active Search and Examination
  • 1995-11-01 CA CA002161945A patent/CA2161945A1/fr not_active Abandoned
  • 1995-11-01 AR AR33407895A patent/AR000056A1/es unknown
  • 1995-11-02 JP JP7309801A patent/JPH08208731A/ja active Pending
  • 1995-11-02 CN CN95118129A patent/CN1133299A/zh active Pending
  • 1995-11-02 ZA ZA959247A patent/ZA959247B/xx unknown

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